烯类单体自由基加聚反应的链增长过程,主要是链自由基和单体形成过渡态时π分子轨道的变化过程。因此如能计算出变化时π分子轨道的能级,就可以得出变化过程中π电子的能量曲线,从而与加聚反应的活化能相联系.前人的工作是应用定域理论计算反应前后共振能的变化,或用微扰理论计算微扰能,以此来和链增长反应的活化能相联系.他们这些方法 The chain growth process of the radical polymerization of vinyl monomers is mainly the change of π molecular orbitals when the chain radical and monomer form a transition state. Therefore, if we can calculate the energy level of π molecular orbitals during the change, we can get the energy curve of π electron during the change, which is related to the activation energy of polyaddition reaction. These changes in resonance energy, or the perturbation theory, can be used to calculate the perturbation energy to correlate with the activation energy of the chain growth reaction. These methods